Stabilizer mixture

ABSTRACT

Suitable stabilizers for organic material are a mixture comprising A. at least one oligomeric compound, comprising repeat units of the formula (I), in which the meanings of the symbols are as follows: R1 is hydrogen, C1-C6-alkyl, formyl, C2-C6-alkanoyl, C1-C12-alkoxy, C5-C6-cycloalkoxy, cyanomethyl, 2-hydroxyethyl, benzyl or a radical of the formula -CR&#39;=CH-CO-OR&#39;&#39;, where R&#39; is hydrogen, C1-C6-alkyl or a radical of the formula -CO-OR&#39;&#39;, and R&#39;&#39; is C1-C18-alkyl, C5-C8-cycloalkyl, C7-C18-aralkyl, phenyl, or tolyl; R2 is a mixture composed of C14-C25-alkyl groups, where two of these alkyl groups whose number of carbon atoms is not permitted to differ by more than two respectively make up at least 30% of this mixture; R3 and R4, independently of one another, are C1-C6-alkyl; and B. at least one compound of the formula (II) or (III) where the meanings of the symbols and indices are as follows: n and m, independently of one another, are a natural number from 2 to 22, and R1, R3 and R4, independently of one another, have the meanings given in formula (I).

REFERENCE TO PRIOR APPLICATIONS

This application is a Continuation of U.S. application Ser. No.13/874,619, filed May 1, 2013, which is a Divisional of U.S. applicationSer. No. 12/160,724, filed Jul. 11, 2008; which is a 371 ofPCT/EP07/50281, filed Jan. 12, 2007, the text of which is herebyincorporated by reference, and claims foreign priority to Europeanpatent application 06100343.0 filed Jan. 13, 2006, the entire content ofwhich is incorporated herein by reference.

DESCRIPTION

The invention relates to a mixture composed of oligomeric and monomericcompounds of HALS type, to a process for their preparation, and also totheir use as stabilizers for organic material.

Organic material, in particular plastics and paints, is known todecompose very rapidly, especially via exposure to light. Thisdecomposition is usually apparent from yellowing, discoloration,cracking, or embrittlement of the material. Light stabilizers and otherstabilizers are therefore intended to achieve satisfactory prevention ofdecomposition of organic material via light, oxygen, and heat.

Derivatives of 2,2,6,6-tetraalkylpiperidine, termed HALS (Hindered AmineLight Stabilizers), have been used commercially now for about thirtyyears as light stabilizers and other stabilizers, in particular forplastics and paints.

WO 94/12544 describes maleimide-α-olefin copolymers which have HALSgroups as substituents, features of these copolymers being not only thelack of any tendency toward migration within the material to beprotected but also good compatibility with the usual types of plastic,and good solubility, and excellent compatibility in the usual paintsystems.

Although these compounds are now achieving excellent success inpractical commercial use, there is nevertheless room for improvement, inparticular with regard to storage properties and transport properties.

It is therefore an object to provide further improved light stabilizers,in particular with improved storage properties and improved transportproperties.

The object is achieved via a mixture of the oligomeric HALS describedabove with certain low-molar-mass (M<1000 g/mol) HALS. The inventivemixture firstly has increased, synergistic stabilizing action andsecondly exhibits improved storage properties and improved transportproperties, because, unlike the oligomeric compounds alone, it has notendency toward caking on storage. The inventive mixture does nottherefore need to be diluted with diluents, such as fumed silica,silicates, alkaline earth metal stearates, or talc.

Mixtures of oligomeric and low-molecular-weight HALS are previouslyknown, for example in the form of Tinuvin® 791 from Ciba SpecialtyChemicals, but these involve structurally different oligomeric compoundswhich cannot lead to any conclusion concerning any advantageous actionof the inventive mixture.

The invention therefore provides a mixture, comprising

A. at least one oligomeric compound, comprising repeat units of theformula (I),

-   -   in which the meanings of the symbols are as follows:    -   R¹ is hydrogen, C₁-C₆-alkyl, formyl, C₂-C₆-alkanoyl,        C₁-C₁₂-alkoxy, C₅-C₆-cycloalkoxy, cyanomethyl, 2-hydroxyethyl,        benzyl or a radical of the formula —CR′═CH—CO—OR″, where    -   R′ is hydrogen, C₁-C₆-alkyl or a radical of the formula —CO—OR″,        and    -   R″ is C₁-C₁₈-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₈-aralkyl, phenyl, or        tolyl;    -   R² is a mixture composed of C₁₄-C₂₈-alkyl groups, where two of        these alkyl groups whose number of carbon atoms is not permitted        to differ by more than two respectively make up at least 30% of        this mixture;    -   R³ and R⁴, independently of one another, are C₁-C₆-alkyl;    -   and

B. at least one compound of the formula (II) or (III)

-   -   where the meanings of the symbols and indices are as follows:    -   n and m, independently of one another, are a natural number from        2 to 22,    -   and    -   R¹, R³ and R⁴, independently of one another, have the meanings        given in formula (I).

The inventive mixtures are used for stabilization of organic material,in particular of polymers, with respect to the effect of light.

The average molecular weight of the oligomers (A) is generally from 1000to 50 000, preferably from 1500 to 10 000, in particular from 2000 to5000. The molecular weights given are number-average molecular weights.

The average number of repeat units is from 3 to 100, preferably from 4to 30, in particular from 5 to 10.

The radical R¹ is preferably H, C₁-C₆-alkyl, formyl, acyl, C₁-C₆-alkoxy,or benzyl, particularly preferably H, methyl, formyl, acyl or benzyl, inparticular H.

The radical R² is a mixture composed of C₁₄-C₂₈-alkyl groups, preferablyC₁₆-C₂₄-alkyl groups, in particular C₁₈-C₂₂-alkyl groups, and the unitson which the copolymer is based are therefore C₁₆-C₃₀ α-olefins,preferably C₁₈-C₂₆ α-olefins, in particular C₂₀-C₂₄ α-olefins. R² ispreferably linear alkyl groups.

The presence of a mixture of alkyl groups for R² means that, when astatistical average is taken across the entire number of all of thecopolymer molecules present, two particular alkyl groups whose number ofcarbon atoms is not permitted to differ by more than two respectivelymake up at least 30%, preferably respectively make up at least 40%, ofthis mixture. These are in particular mixtures of 3 particular alkylgroups, e.g. octadecyl, eicosyl, and docosyl, where two of these groupswhose number of carbon atoms differs by 2 make up more than 40% of themixture, and the third group makes up from 3 to 18% of the mixture;other alkyl groups having somewhat fewer than 18 or somewhat more than22 carbon atoms can be present in the mixture here; their amounts beingvery small, usually less than 2%.

If not otherwise stated percentages refer to percent by weight.

The radicals R³ and R⁴ are preferably C₁-C₄-alkyl, particularlypreferably methyl, and the meaning of all of the radicals R³ and R⁴ isin particular respectively methyl.

Alkyl radicals that can be used and are claimed in the form of C₁-C₆(for R³ and R⁴) and C₁-C₁₅ (for R″) are branched, and in particularstraight-chain members of the group, and therefore especially methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,n-amyl, isoamyl, sec-amyl, tert-amyl, neopentyl, n-hexyl, n-heptyl,n-octyl, 2-ethylhexyl, 2-propylheptyl, n-nonyl, isononyl, n-decyl,n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.

Straight-chain or branched C₂-C₆-alkanoyl that can be used for R¹ isespecially acetyl, but also propionyl, butyryl, isobutyryl, pentanoyl,and hexanoyl.

Especially suitable straight-chain or branched C₁-C₁₂-alkoxy groups forR¹ are C₆-C₈-alkoxy groups, such as n-hexoxy, isohexoxy, n-octoxy,2-ethylhexoxy, and isooctoxy, but also methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy,n-nonoxy, n-decoxy, n-undecoxy, and n-dodecoxy.

C₅-C₆-cycloalkoxy groups for R¹ are especially cyclopentoxy andcyclohexoxy.

C₅-C₈-cycloalkyl radicals that can be used for R″ are especiallycyclopentyl and cyclohexyl, but also cycloheptyl, cyclooctyl,methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl,ethylcyclohexyl, and dimethylcyclohexyl.

Examples of suitable C₇-C₁₈-aralkyl radicals for R″ are naphthylmethyl,diphenylmethyl, or methylbenzyl, but in particular C₇-C₁₈-phenylalkyl,such as 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 2-phenylprop-2-yl, 4-phenylbutyl,2,2-dimethyl-2-phenylethyl, 5-phenylamyl, 10-phenyldecyl,12-phenyldodecyl, or preferably benzyl.

Tolyl radicals that can be used are ortho-, meta-, and preferablyp-tolyl.

An oligomer having the repeat unit (Ia) whose number-average molar massis from 3000 to 4000 g/mol is particularly preferred as oligomericcomponent A

A compound of this type is obtainable as Uvinul® 5050 H from BASFAktiengesellschaft, Ludwigshafen, Germany.

If the oligomeric component (A) is not obtainable commercially, thecompounds can be prepared by the methods given in WO 94/12544.

Among the low-molecular-weight compounds (II) and (III) of component(B), preference is given to those in which the meanings of the symbolsand indices are as follows:

-   -   R¹ is preferably H, C₁-C₄-alkyl, formyl, acyl, or benzyl,        particularly preferably H, methyl, formyl, acyl, or benzyl,        especially preferably H.    -   R³ and R⁴ are preferably C₁-C₄-alkyl, particularly preferably        methyl, and especially preferably all of the radicals R³ and R⁴        are methyl.    -   m and n are preferably a natural number from 4 to 10,        particularly preferably 6 or 8, and especially preferably m is        the number 6 and n is the number 8.

Preferred are compounds (II) and (III) in which the symbols and indiceshave the preferred meanings. Particularly preferred are the compounds(II) and (III) in which the symbols and indices have the particularlypreferred meanings. Especially preferred are compounds (II) and (III)where the symbols and indices have the especially preferred meanings.

The compounds (IIa), (IIIa), and (IIIb) are particularly preferred ascompounds of component (B)

these being commercially obtainable as Uvinul® 4050 H and Uvinul® 4077 Hfrom BASF Aktiengesellschaft, Ludwigshafen, Germany.

The compound (IIa) is particularly preferred as component B.

If the compounds of the formula (II) are not commercially obtainable,they can be prepared by the methods described in EP-A 0 316 582.

If the compounds of the formula (III) are not commercially obtainable,they can be prepared by methods that are known and familiar to theperson skilled in the art, for example via esterification of sebacicesters with 2,2,6,6-tetraalkylpiperidin-4-ol derivatives.

The ratio by weight of components (A) and (B) in the inventive mixturesis generally from 5:1 to 1:5, preferably from 2:1 to 1:2, particularlypreferably from 1.2:1 to 1:1.2, and particular preference is given to amixture whose ratio by weight is about 1:1.

The inventive mixtures can be prepared by processes that are known andfamiliar to the person skilled in the art.

Component (B) can preferably be added to a melt of component (A), andthe mixture can be homogenized, and converted to the desired form, forexample pastilles, and allowed to cool.

The invention therefore also provides a respective process forpreparation of the inventive mixtures.

However, it is also possible to mix solutions of the two components (A)and (B) and then to remove the solvent(s).

The following combinations of compounds of components (A) and (B) areparticularly preferred:

-   -   a) the combination of the compounds (Ia) and (IIa),    -   b) the combination of the compounds (Ia) and (IIIa),    -   c) the combination of the compounds (Ia) and (IIIb).

The combination (a) is particularly preferred.

The inventive mixtures have excellent suitability for use as stabilizersfor stabilization of organic material (preferably not of living organicmaterial) with respect to exposure to light, oxygen, and heat. They areadded at a concentration of from 0.01 to 5% by weight, preferably from0.02 to 1% by weight, based on the organic material, to the organicmaterials to be stabilized, prior to, during, or after theirpreparation.

The inventive mixture can be added to the organic material to beprotected in the form of a prefabricated mixture of components (A) and(B), but another possibility is separate addition of components (A) and(B) to the material to be protected, in which case the mixture is notproduced until the components are present within the material to beprotected. In the event of separate addition of components (A) and (B),this can take place simultaneously or non-simultaneously, and thesequence here is not generally significant.

Examples of organic material are cosmetic preparations, such asointments and lotions, pharmaceutical formulations, such as pills andsuppositories, photographic recording material, such as photographicemulsions, or precursors for plastics and paints, but in particularplastics and paints themselves.

The invention also provides an organic material stabilized with respectto exposure to light, oxygen, and heat, in particular a plastic orpaint, where the material comprises an inventive mixture, preferably atthe concentrations given above.

Any of the known apparatus and methods for mixing to incorporatestabilizers or other additives into polymers can be used for mixing ofthe inventive mixture, particularly with plastics.

The inventive mixture, or the organic material to be stabilized via themixture, optionally also comprises at least one further light stabilizerand/or other (co)stabilizers. By way of example, suitable lightstabilizers and other (co)stabilizers are those selected from the groupsa) to s):

-   a) 4,4-diarylbutadienes,-   b) cinnamates,-   c) benzotriazoles,-   d) hydroxybenzophenones,-   e) diphenylcyanoacrylates,-   f) oxamides,-   g) 2-phenyl-1,3,5-triazines,-   h) antioxidants,-   i) nickel compounds,-   j) further sterically hindered amines,-   k) metal deactivators,-   l) phosphites and phosphonites,-   m) hydroxylamines,-   n) nitrones,-   o) amine oxides,-   p) benzofuranones and indolinones,-   q) thiosynergists,-   r) peroxide-destroying compounds and-   s) basic costabilizers.

The group a) of the 4,4-diarylbutadienes includes, for example,compounds of the formula (aa)

The compounds are known from EP-A 916 335. The R⁵ and/or R⁶ substituentsare preferably C₁-C₈-alkyl and C₅-C₈-cycloalkyl.

The group b) of the cinnamates includes, for example, 2-isoamyl4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methylα-(methoxycarbonyl)cinnamate, methylα-cyano-(3-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate and methylα-(methoxycarbonyl)-p-methoxycinnamate.

The group c) of the benzotriazoles includes, for example,2-(2′-hydroxyphenyl)benzotriazoles, such as2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di(tert-butyl)-2′-hydroxyphenyl)benzotriazole,2-(5′-(tert-butyl)-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di(tert-butyl)-2′-hydroxyphenyI)-5-chlorobenzotriazole,2-(3′-(tert-butyl)-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-(sec-butyl)-5′-(tert-butyl)-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di(tert-amyl)-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-(tert-butyl)-5′-[2-(2-ethylhexyloxycarbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-(tert-butyl)-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-isooctyloxy-carbonylethyl)phenyl)benzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(benzotriazol-2-yl)phenol],the product of esterification of2-[3′-(tert-butyl)-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300, [R—CH₂CH₂—COO(CH₂)₃]₂, whereR=3′-(tert-butyl)-4′-hydroxy-5′-(2H-benzotriazol-2-yl)phenyl, andmixtures thereof.

The group d) of the hydroxybenzophenones includes, for example,2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone,2,2′-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone,2,2′,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone,2-hydroxy-4-(2-ethylhexyloxy)benzophenone,2-hydroxy-4-(n-octyloxy)benzophenone,2-hydroxy-4-methoxy-4′-methylbenzophenone,2-hydroxy-3-carboxybenzophenone,2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, and2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-disulfonic acid and itssodium salt.

The group e) of the diphenylcyanoacrylates includes, for example, ethyl2-cyano-3,3-diphenylacrylate, which, for example, is obtainablecommercially as Uvinul® 3035 from BASF Aktiengesellschaft, Ludwigshafen,2-ethylhexyl 2-cyano-3,3-diphenylacrylate, which, for example, isobtainable commercially as Uvinul® 3039 from BASF Aktiengesellschaft,Ludwigshafen, and1,3-bis[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis{[(2′-cyano-3′,3′-diphenyl-acryloyl)oxy]methyl}propane,which, for example, is obtainable commercially as Uvinul® 3030 from BASFAktiengesellschaft, Ludwigshafen.

The group f) of the oxamides includes, for example,4,4′-dioctyloxyoxanilide, 2,2′-di-ethoxyoxanilide,2,2′-dioctyloxy-5,5′-di(tert-but)oxanilide,2,2′-didodecyloxy-5,5′-di(tert-but)oxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-(tert-butyl)-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di(tert-but)oxanilide, and also mixtures ofortho- and para-methoxy-disubstituted oxanilides and mixtures of ortho-and para-ethoxy-disubstituted oxanilides.

The group g) of the 2-phenyl-1,3,5-triazines includes, for example,2-(2-hydroxyphenyl)-1,3,5-triazines, such as2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-(butyloxy)propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-(octyloxy)propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-(dodecyloxy)propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazineand 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

The group h) of the antioxidants comprises, for example:

-   -   h.1) alkylated monophenols, for example        2,6-di(tert-butyl)-4-methylphenol,        2-(tert-butyl)-4,6-dimethylphenol,        2,6-di(tert-butyl)-4-ethylphenol,        2,6-di(tert-butyl)-4-(n-butyl)phenol,        2,6-di(tert-butyl)-4-isobutylphenol,        2,6-dicyclopentyl-4-methylphenol,        2-(α-methylcyclohexyl)-4,6-dimethylphenol,        2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,        2,6-di(tert-butyl)-4-methoxymethylphenol, unbranched        nonylphenols or nonylphenols which are branched in the side        chain, such as, for example, 2,6-dinonyl-4-methylphenol,        2,4-dimethyl-6-(1-methylundec-1-yl)phenol,        2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,        2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.    -   h.2) Alkylthiomethylphenols, for example        2,4-dioctylthiomethyl-6-(tert-butyl)phenol,        2,4-dioctylthiomethyl-6-methylphenol,        2,4-dioctylthiomethyl-6-ethylphenol and        2,6-didodecylthiomethyl-4-nonylphenol.    -   h.3) Hydroquinones and alkylated hydroquinones, for example        2,6-di(tert-butyl)-4-methoxyphenol,        2,5-di(tert-butyl)hydroquinone, 2,5-di(tert-amyl)hydroquinone,        2,6-diphenyl-4-octadecyloxyphenol,        2,6-di(tert-butyl)hydroquinone,        2,5-di(tert-butyl)-4-hydroxyanisole,        3,5-di(tert-butyl)-4-hydroxyanisole,        3,5-di(tert-butyl)-4-hydroxyphenyl stearate and        bis(3,5-di(tert-butyl)-4-hydroxyphenyl) adipate.    -   h.4) Tocopherols, for example α-tocopherol, β-tocopherol,        γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).    -   h.5) Hydroxylated thiodiphenyl ethers, for example        2,2′-thiobis(6-(tert-butyl)-4-methylphenol),        2,2′-thiobis(4-octylphenol),        4,4′-thiobis(6-(tert-butyl)-3-methylphenol),        4,4′-thiobis(6-(tert-butyl)-2-methylphenol),        4,4′-thiobis(3,6-di(sec-amyl)phenol) and        4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.    -   h.6) Alkylidenebisphenols, for example        2,2′-methylenebis(6-(tert-butyl)-4-methylphenol),        2,2′-methylenebis(6-(tert-butyl)-4-ethylphenol),        2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],        2,2′-methylenebis(4-methyl-6-cyclohexylphenol),        2,2′-methylenebis(6-nonyl-4-methylphenol),        2,2′-methylenebis(4,6-di(tert-butyl)phenol),        2,2′-ethylidenebis(4,6-di(tert-butyl)phenol),        2,2′-ethylidenebis(6-(tert-butyl)-4-isobutylphenol),        2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],        2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],        4,4′-methylenebis(2,6-di(tert-butyl)phenol),        4,4′-methylenebis(6-(tert-butyl)-2-methylphenol),        1,1-bis(5-(tert-butyl)-4-hydroxy-2-methylphenyl)butane,        2,6-bis(3-(tert-butyl)-5-methyl-2-hydroxybenzyl)-4-methylphenol,        1,1,3-tris(5-(tert-butyl)-4-hydroxy-2-methylphenyl)butane,        1,1-bis(5-(tert-butyl)-4-hydroxy-2-methylphenyl)-3-(n-dodecylmercapto)butane,        ethylene glycol        bis[3,3-bis(3-(tert-butyl)-4-hydroxyphenyl)butyrate],        bis(3-(tert-butyl)-4-hydroxy-5-methylphenyl)dicyclopentadiene,        bis[2-(3′-(tert-butyl)-2-hydroxy-5-methylbenzyl)-6-(tert-butyl)-4-methylphenyl]        terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,        2,2-bis(3,5-di(tert-butyl)-4-hydroxyphenyl)propane,        2,2-bis(5-(tert-butyl)-4-hydroxy-2-methylphenyl)-4-(n-dodecylmercapto)butane        and        1,1,5,5-tetra(5-(tert-butyl)-4-hydroxy-2-methylphenyl)pentane.    -   h.7) Benzyl compounds, for example        3,5,3′,5′-tetra(tert-butyl)-4,4′-dihydroxydibenzyl ether,        octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl        4-hydroxy-3,5-di(tert-butyl)benzylmercaptoacetate,        tris(3,5-di(tert-butyl)-4-hydroxybenzyl)amine,        1,3,5-tri(3,5-di(tert-butyl)-4-hydroxybenzyl)-2,4,6-trimethylbenzene,        di(3,5-di(tert-butyl)-4-hydroxybenzyl) sulfide, isooctyl        3,5-di(tert-butyl)-4-hydroxybenzylmercaptoacetate,        bis(4-(tert-butyl)-3-hydroxy-2,6-dimethylbenzyl)        dithioterephthalate,        1,3,5-tris(3,5-di(tert-butyl)-4-hydroxybenzyl) isocyanurate,        1,3,5-tris(4-(tert-butyl)-3-hydroxy-2,6-dimethylbenzyl)        isocyanurate, 3,5-di(tert-butyl)-4-hydroxybenzyl dioctadecyl        phosphate and 3,5-di(tert-butyl)-4-hydroxybenzyl monoethyl        phosphate, calcium salt.    -   h.8) Hydroxybenzylated malonates, for example dioctadecyl        2,2-bis(3,5-di(tert-butyl)-2-hydroxybenzyl)malonate, dioctadecyl        2-(3-(tert-butyl)-4-hydroxy-5-methylbenzyl)malonate,        didodecylmercaptoethyl        2,2-bis(3,5-di(tert-butyl)-4-hydroxybenzyl)malonate and        bis[4-(1,1,3,3-tetramethylbutyl)phenyl]        2,2-bis(3,5-di(tert-butyl)-4-hydroxybenzyl)malonate.    -   h.9) Hydroxybenzyl aromatic compounds, for example        1,3,5-tris(3,5-di(tert-butyl)-4-hydroxybenzyl)-2,4,6-trimethylbenzene,        1,4-bis(3,5-di(tert-butyl)-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene        and 2,4,6-tris(3,5-di(tert-butyl)-4-hydroxybenzyl)phenol.    -   h.10) Triazine compounds, for example        2,4-bis(octylmercapto)-6-(3,5-di(tert-butyl)-4-hydroxyanilino)-1,3,5-triazine,        2-octylmercapto-4,6-bis(3,5-di(tert-butyl)-4-hydroxyanilino)-1,3,5-triazine,        2-octylmercapto-4,6-bis(3,5-di(tert-butyl)-4-hydroxyphenoxy)-1,3,5-triazine,        2,4,6-tris(3,5-di(tert-butyl)-4-hydroxyphenoxy)-1,3,5-triazine,        1,3,5-tris(3,5-di(tert-butyl)-4-hydroxybenzyl) isocyanurate,        1,3,5-tris(4-(tert-butyl)-3-hydroxy-2,6-dimethylbenzyl)        isocyanurate,        2,4,6-tris(3,5-di(tert-butyl)-4-hydroxyphenylethyl)-1,3,5-triazine,        1,3,5-tris(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine        and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.    -   h.11) Benzylphosphonates, for example dimethyl        2,5-di(tert-butyl)-4-hydroxybenzylphosphonate, diethyl        3,5-di(tert-butyl)-4-hydroxybenzylphosphonate        ((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methylphosphonic        acid diethyl ester), dioctadecyl        3,5-di(tert-butyl)-4-hydroxybenzylphosphonate, dioctadecyl        5-(tert-butyl)-4-hydroxy-3-methylbenzylphosphonate and calcium        salt of 3,5-di(tert-butyl)-4-hydroxybenzylphosphonic acid        monoethyl ester.    -   h.12) Acylaminophenols, for example lauric acid        4-hydroxyanilide, stearic acid 4-hydroxyanilide,        2,4-bisoctylmercapto-6-(3,5-(tert-butyl)-4-hydroxyanilino)-s-triazine        and octyl N-(3,5-di(tert-butyl)-4-hydroxyphenyl)carbamate.    -   h.13) Esters of β-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionic        acid with mono- or polyhydric alcohols, such as, e.g., with        methanol, ethanol, n-octanol, isooctanol, octadecanol,        1,6-hexanediol, 1,9-nonanediol, ethylene glycol,        1,2-propanediol, neopentyl glycol, thiodiethylene glycol,        diethylene glycol, triethylene glycol, pentaerythritol,        tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl) oxalic        acid diamide, 3-thiaundecanol, 3-thiapentadecanol,        trimethylhexanediol, trimethylolpropane and        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    -   h.14) Esters of        β-(5-(tert-butyl)-4-hydroxy-3-methylphenyl)propionic acid with        mono- or polyhydric alcohols, such as, e.g., with methanol,        ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol,        1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl        glycol, thiodiethylene glycol, diethylene glycol, triethylene        glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,        N,N′-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol,        3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2] octane.    -   h.15) Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic        acid with mono- or polyhydric alcohols, such as, e.g., with        methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,        1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl        glycol, thiodiethylene glycol, diethylene glycol, triethylene        glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,        N,N′-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol,        3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    -   h.16) Esters of 3,5-di(tert-butyl)-4-hydroxyphenylacetic acid        with mono- or polyhydric alcohols, such as, e.g., with methanol,        ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,        ethylene glycol, 1,2-propanediol, neopentyl glycol,        thiodiethylene glycol, diethylene glycol, triethylene glycol,        pentaerythritol, tris(hydroxyethyl) isocyanurate,        N,N′-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol,        3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    -   h.17) Amides of β-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionic        acid, such as, e.g.,        N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hexamethylenediamine,        N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)trimethylenediamine,        N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hydrazine        and        N,N′-bis[2-(3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionyloxy)ethyl]oxamide        (e.g. Naugard®XL-1 from Uniroyal).    -   h.18) Ascorbic acid (vitamin C)    -   h.19) Aminic antioxidants, such as        N,N′-diisopropyl-p-phenylenediamine,        N,N′-di(sec-butyl)-p-phenylenediamine,        N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,        N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,        N,N′-bis(1-methylheptyl)-p-phenylenediamine,        N,N′-dicyclohexyl-p-phenylenediamine,        N,N′-diphenyl-p-phenylenediamine,        N,N′-bis(2-naphthyl)-p-phenylenediamine,        N-isopropyl-N′-phenyl-p-phenylenediamine,        N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,        N-(1-methylheptyI)-N′-phenyl-p-phenylenediamine,        N-cyclohexyl-N′-phenyl-p-phenylenediamine,        4-(p-tolylsulfamoyl)diphenylamine,        N,N′-dimethyl-N,N′-di(sec-butyl)-p-phenylenediamine,        diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine,        N-phenyl-1-naphthylamine,        N-(4-(tert-octyl)phenyl)-1-naphthylamine,        N-phenyl-2-naphthylamine, octylated diphenylamine, e.g.        p,p′-di(tert-octyl)diphenylamine, 4-(n-butylamino)phenol,        4-butyrylaminophenol, 4-nonanoylaminophenol,        4-dodecanoylaminophenol, 4-octadecanoylaminophenol,        bis(4-methoxyphenyl)amine,        2,6-di(tert-butyl)-4-dimethylaminomethylphenol,        2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,        N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,        1,2-bis[(2-methylphenyl)amino]ethane,1,2-bis(phenylamino)propane,        (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,        tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and        dialkylated tert-butyl/tert-octyldiphenylamines, mixture of        mono- and dialkylated nonyldiphenylamines, mixture of mono- and        dialkylated dodecyldiphenylamines, mixture of mono- and        dialkylated isopropyl/isohexyldiphenylamines, mixture of mono-        and dialkylated tert-butyldiphenylamines,        2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,        mixture of mono- and dialkylated        tert-butyl/tert-octylphenothiazines, mixture of mono- and        dialkylated tert-octylphenothiazines, N-allylphenothiazine,        N,N,N′,N¹-tetraphenyl-1,4-diaminobut-2-ene,        N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine,        2,2,6,6-tetramethylpiperidin-4-one,        2,2,6,6-tetramethylpiperidin-4-ol, the dimethyl succinate        polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol        [CAS number 65447-77-0] (for example Tinuvin® 622 from Ciba        Specialty Chemicals Inc.) and the polymer of        2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one        and epichlorohydrin [CAS-No.: 202483-55-4] (for example        Hostavin® N 30 from Clariant).

The group i) of the nickel compounds includes, for example, nickelcomplexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenols], such asthe 1:1 or 1:2 complex, if appropriate with additional ligands, such asn-butylamine, triethanolamine, or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl4-hydroxy-3,5-di-tert-butylbenzylphosphonates, e.g. the methyl or ethylester, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complex of1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additionalligands.

The group j) of the sterically hindered amines includes, for example,4-hydroxy-2,2,6,6-tetramethylpiperidine,1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)(n-butyl)(3,5-di(tert-butyl)-4-hydroxybenzyl)malonate((n-butyl)(3,5-di(tert-butyl)-4-hydroxybenzyl)malonic acidbis(1,2,2,6,6-pentamethylpiperidyl) ester), condensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensation products ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-(tert-octylamino)-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)2-(n-butyl)-2-(2-hydroxy-3,5-di(tert-butyl)benzyl)malonate,3-(n-octyl)-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cycliccondensation products ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and formicacid ester (CAS No. 124172-53-8, e.g. Uvinul® 4050 H from BASFAktiengesellschaft, Ludwigshafen), condensation product of2-chloro-4,6-bis(4-(n-butyl)amino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, condensation product of2-chloro-4,6-di(4-(n-butyl)amino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]);N-(2,2,6,6-tetramethyl-4-piperidyl)(n-dodecyl)succinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)(n-dodecyl)succinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]-decane,reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxo-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic anhydride/α-olefin copolymer and2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine,the reaction product of 1-oxy-4-hydroxy-2,2,6,6-tetramethylpiperidineand a carbon radical of Cert-amyl alcohol,1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate,2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine,N,N′-bisformyl-N,N′-bis(1,2,2,6,6-pentamethyl-4-piperidyl)hexamethylenediamine,hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidyl)-1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacyclopenta[def]fluorene-4,8-dione(e.g. Uvinul® 4049 from BASF Aktiengesellschaft, Ludwigshafen),poly[[6[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]][CAS No. 71878-19-8] or 1,3,5-triazine-2,4,6-triamine,N,N′″-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]-bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-(CAS No. 106990-43-6) (e.g. Chimassorb 119 from Ciba Specialty ChemicalsInc.).

The group k) of the metal deactivators includes, for example,N,N′-diphenyloxamide, N-salicylal-N′-salicyloylhydrazine,N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, the bis(benzylidene) derivative ofoxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacicbisphenylhydrazide, N,N′-diacetyladipic acid dihydrazide,N,N′-bis(salicyloyl)oxalic acid dihydrazide orN,N′-bis(salicyloyl)thiopropionic dihydrazide.

The group l) of the phosphites and phosphonites includes, for example,triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkylphosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,trioctadecyl phosphite, distearyl pentaerythritol diphosphite,tris(2,4-di(tert-butyl)phenyl) phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di(tert-butyl)phenyl) pentaerythritol diphosphite,bis(2,6-di(tert-butyl)-4-methylphenyl) pentaerythritol diphosphite,diisodecyloxy pentaerythritol diphosphite,bis(2,4-di(tert-butyl)-6-methylphenyl) pentaerythritol diphosphite,bis(2,4,6-tris(tert-butyl)phenyl) pentaerythritol diphosphite,tristearyl sorbitol triphosphite, tetrakis(2,4-di(tert-butyl)phenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra(tert-butyl)dibenzo[d,f][1,3,2]dioxaphosphepin,6-fluoro-2,4,8,10-tetra(tert-butyl)-12-methyldibenzo[d,g][1,3,2]dioxaphosphocin,bis(2,4-di(tert-butyl)-6-methylphenyl) methyl phosphite,bis(2,4-di(tert-butyl)-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra(tert-butyl)-1,1′-biphenyl-2,2′-diyl) phosphite] and2-ethylhexyl (3,3′,5,5′-tetra(tert-butyl)-1,1′-biphenyl-2,2′-diyl)phosphite.

The group m) of the hydroxylamines includes, for example,N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamineand N,N-dialkylhydroxylamine from hydrogenated tallow fatty amines.

The group n) of the nitrones includes, for example,N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone,N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone,N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone,N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone,N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone,N-octadecyl-α-hexadecylnitrone, N-methyl-α-heptadecylnitrone andnitrones derived from N,N-dialkylhydroxylamines prepared fromhydrogenated tallow fatty amines.

The group o) of the amine oxides includes, for example, amine oxidederivatives as disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191,didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide andtrihexadecylamine oxide.

The group p) of the benzofuranones and indolinones includes, forexample, those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244,5,175,312, 5,216,052 or 5,252,643, in DE-A-4316611, in DE-A-4316622, inDE-A-4316876, in EP-A-0589839 or in EP-A-0591102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di(tert-butyl)benzofuran-2-one,5,7-di(tert-butyl)-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di(tert-butyl)-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di(tert-butyl)-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di(tert-butyl)benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di(tert-butyl)benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di(tert-butyl)benzofuran-2-one, IrganoxsHP-136 from Ciba Specialty Chemicals and3-(2,3-dimethylphenyl)-5,7-di(tert-butyl)benzofuran-2-one.

The group q) of the thiosynergists includes, for example, dilaurylthiodipropionate or distearyl thiodipropionate.

The group r) of the peroxide-destroying compounds includes, for example,esters of β-thiodipropionic acid, e.g. the lauryl, stearyl, myristyl ortridecyl ester, mercaptobenzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide or pentaerythritol tetrakis(β-dodecylmercaptopropionate).

The group s) of the basic costabilizers includes, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,the alkali metal and alkaline earth metal salts of higher fatty acids,e.g. calcium stearate, zinc stearate, magnesium behenate, magnesiumstearate, sodium ricinoleate, and potassium palmitate, antimonypyrocatecholate or zinc pyrocatecholate.

The plastic can moreover comprise other additives and added materials.Suitable additives of group t) that can be used are the conventionaladded materials, e.g. pigments, dyes, nucleating agents, fillers orreinforcing agents, antifogging agents, biocides, and antistatic agents.

Suitable pigments are inorganic pigments, such as titanium dioxide inits three crystalline forms: rutile, anatase, or brookite, ultramarineblue, iron oxides, bismuth vanadates, or carbon black, and also theclass of the organic pigments, for example compounds from the class ofthe phthalocyanines, perylenes, azo compounds, isoindolines,quinophthalones, diketopyrrolopyrroles, quinacridones, dioxazines,indanthrones.

Dyes are any of the colorants which dissolve completely in the plasticused or are present in molecularly dispersed form and therefore can beused to provide high-transparency, non-diffusion coloring of polymers.Other dyes are organic compounds which fluoresce in the visible portionof the electromagnetic spectrum, e.g. fluorescent dyes.

Suitable nucleating agents comprise, for example, inorganic substances,such as talc, metal oxides, such as titanium dioxide or magnesium oxide,phosphates, carbonates, or sulfates, preferably of alkaline earthmetals; organic compounds, such as mono- or polycarboxylic acids, andalso their salts, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate, or sodium benzoate; polymericcompounds, such as ionic copolymers (“ionomers”).

Suitable fillers or reinforcing materials comprise, for example, calciumcarbonate, silicates, talc, mica, kaolin, barium sulfate, metal oxides,metal hydroxides, carbon black, graphite, wood flour, and flours orfibers composed of other natural products, and synthetic fibers. Otherexamples of fibrous or pulverulent fillers that can be used are carbonfibers or glass fibers in the form of glass textiles, glass mats, orglass silk rovings, chopped glass, glass beads, and also wollastonite.Glass fibers can be incorporated in the form of short glass fibers orelse in the form of continuous-filament fibers (rovings).

Examples of suitable antistatic agents are amine derivatives, such asN,N-bis-(hydroxyalkyl)alkylamines or -alkyleneamines, polyethyleneglycol esters and polyethylene glycol ethers, ethoxylated carboxylicesters and ethoxylated carboxamides, and glycerolmono- and distearates,and also mixtures of these.

Examples which may be mentioned of plastics which can be stabilized viathe inventive mixtures are:

polymers of mono- and diolefins, e.g. low- and high-densitypolyethylene, polypropylene, linear poly-1-butene, polyisoprene,polybutadiene, and also copolymers of mono- or diolefins, and mixturesof the polymers mentioned;

copolymers of mono- or diolefins with other vinyl monomers, e.g.ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylatecopolymers, ethylene-vinyl acetate copolymers, or ethylene-acrylic acidcopolymers;

polystyrene, and also copolymers of styrene or α-methylstyrene withdienes and/or with acrylic derivatives, e.g. styrene-butadiene,styrene-acrylonitrile (SAN), styrene-ethyl methacrylate,styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate,acrylonitrile-butadiene-styrene (ABS), or methylmethacrylate-butadiene-styrene (MBS);

halogenated polymers, e.g. polyvinyl chloride, polyvinyl fluoride,polyvinylidene fluoride, and also their copolymers;

polymers which derive from α,β-unsaturated acids and from theirderivatives, e.g. polyacrylates, polymethacrylates, polyacrylamides, andpolyacrylonitriles;

polymers which derive from unsaturated alcohols and amines and,respectively, from their acrylic derivatives or acetals, e.g. polyvinylalcohol and polyvinyl acetate;

polyurethanes, polyamides, polyureas, polyesters, polycarbonates,polysulfones, polyether sulfones, and polyether ketones.

It is also possible to use the inventive mixtures to stabilize paintcoatings, e.g. industrial paints. Among these, the following may beespecially highlighted: stoved finishes, and among these in turn vehiclefinishes, preferably two-layer finishes. Examples of another applicationsector are paints for exterior painting of buildings, of otherstructures, or of industrial apparatus.

The inventive mixtures can be in solid or dissolved form when they areadded to the paint. Their good solubility in paint systems is aparticular advantage here.

The inventive mixtures are preferably used for stabilization ofpolyamides, and also of ABS polymers and of SAN polymers, in particularof molding compositions derived therefrom, and of paint coatings.

Another preferred application sector is stabilization of low- andhigh-density polyethylene, and also of polypropylene and polyamide,including, for example, stabilization of fibers derived therefrom.

The examples provide further illustration of the invention but do notrestrict it.

EXAMPLES

1. Preparation of an Inventive Mixture

500 g ofpoly{3-(eicosyltetracosyl)-1-[2,2,6,6-tetramethylpiperidin-4-yl]pyrrolidine-2,5-dione}(CAS No. 152261-33-1; HALS Ia) were melted by heating and mixed with thesame amount ofN,N′-bisformyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine(CAS No. 124172-53-8; HALS IIa). After homogenization, pastilles wereformed from the hot mixture and solidified on cooling.

2. Storage Stability of the Inventive Mixture

In order to test tendency toward caking,poly{3-(eicosyltetracosyl)-1-[2,2,6,6-tetramethylpiperidin-4-yl]pyrrolidine-2,5-dione}(CAS No. 152261-33-1; HALS Ia), and also the mixture prepared in example1, were stored separately at 40° C. in plastic bags. The specimens wereassessed visually after 20 h.

Specimen Visual assessment after 20 h at 40° C. 1 HALS Ia Cakingthroughout 2 Mixture composed of HALS No caking Ia and HALS IIa (1:1)

The example shows that even under mild conditions the oligomericcomponent A has a tendency toward caking. In contrast to this, theinventive mixture does not cake.

3. Synergistic Action of the Mixture when Compared with the IndividualComponents

3a) Weathering of Colored Polypropylene (PP) Plaques

Red-colored PP plaques with various HALS stabilizers were produced andthen weathered to DIN EN ISO 4892-2. Flexural impact resistance wasmeasured to DIN 53453. The results are shown in the table below:

Flexural impact resistance [mJ/mm²] Stabilizer system*⁾ 0 h 2000 h 3000h 4000 h 1 3000 ppm HALS IIa 45 45 45 45 2 1250 ppm HALS Ia 45 45 46 451250 ppm HALS IIa 3 1250 ppm HALS IVa 44 45 42 40 1250 ppm HALS IVb*⁾HALS IVa: Polymer composed of2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]heneicosan-21-oneand epichlorohydrin (CAS No. 202483-55-4); HALS IVb:2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one(CAS No. 64338-16-5).

From the results it can be seen that the amount of the inventive mixturecomposed of HALS Ia and HALS IIa (serial No. 2) needed is smaller inorder to achieve stabilizing action identical with that achieved withthe low-molecular-weight HALS compound IIa alone (serial No. 1). Fromthe third row it can be seen that other mixtures composed of low- andhigh-molecular-weight HALS compounds have markedly poorer stabilizingaction than the inventive stabilizer mixture.

3b) Stabilization of Polypropylene Tapes

Stretched (1:5) tapes composed of polypropylene with various stabilizerswere produced and weathered to DIN EN ISO 4892-2. The ultimate tensilestrength of the specimens was tested at regular intervals. The specimenwas regarded as decomposed as soon as residual ultimate tensile strengthwas smaller than or equal to 50% of the initial ultimate tensilestrength.

Stabilizer system*⁾ Hours to decomposition 1 1000 ppm HALS Ia 2800 2 500 ppm HALS Ia 3200  500 ppm HALS IIa 3 1000 ppm HALS V 2200 *⁾HALSIa:poly{3-(eicosyltetracosyl)-1-[2,2,6,6-tetramethylpiperidin-4-yl]pyrrolidine-2,5-dione)(CAS No. 152261-33-1); HALS IIa:N,N′-bisformyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine(CAS No. 124172-53-8); HALS V: polymer of4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol and dimethylbutanedioate

1. A mixture, comprising (A) at least one oligomeric compound,comprising repeat units of the formula (I),

wherein: R¹ is hydrogen, C₁-C₆-alkyl, formyl, C₂-C₆-alkanoyl,C₁-C₁₂-alkoxy, C₅-C₆-cycloalkoxy, cyanomethyl, 2-hydroxyethyl, benzyl ora radical of the formula —CR′═CH—CO—OR″, wherein R′ is hydrogen,C₁-C₆-alkyl or a radical of the formula —CO—OR″, and R″ is C₁-C₁₈-alkyl,C₅-C₈-cycloalkyl, C₇-C₁₈-aralkyl, phenyl, or tolyl; R² is a mixturecomposed of C₁₄-C₂₈-alkyl groups, where two of these alkyl groups whosenumber of carbon atoms is not permitted to differ by more than tworespectively make up at least 30% of this mixture; R³ and R⁴,independently of one another, are C₁-C₆-alkyl; and (B) at least onecompound of the formula (II) or (III)

wherein: n and m, independently of one another, are a natural numberfrom 2 to 22, and R¹, R³ and R⁴, independently of one another, have themeanings given are as defined in formula (I).
 2. The mixture accordingto claim 1, wherein: R¹ is H, C₁-C₆-alkyl, formyl, acyl, or benzyl; R²is a mixture composed of C₁₆-C₂₄-alkyl groups; R³ and R⁴ are methyl; andm and n are a natural number from 6 to
 8. 3. The mixture according toclaim 1, wherein component A is an oligomer of formula (Ia):

and component B has been selected from the group of the compounds (IIa),(IIIa), and (IIIb):


4. A process for preparation of a mixture according to claim 1,comprising: a) adding component (B) to a melt of component (A) to obtaina mixture; b) homogenizing the mixture to obtain a resultant mixture;and c) converting the resultant mixture to a desired form and allowingto cool.
 5. An organic material stabilized with respect to exposure tolight, oxygen, and heat, comprising from 0.01 to 5% by weight, based onthe amount of the organic material, of a mixture according to claim 1.6. A plastic or paint stabilized with respect to exposure to light,oxygen, and heat, comprising from 0.01 to 5% by weight, based on theamount of the organic material, of a mixture according to claim
 1. 7.The mixture according to claim 1, wherein the mixture is suitable aslight stabilizers and other stabilizers for organic material.
 8. Themixture according to claim 7, wherein the mixture is suitable as lightstabilizers and other stabilizers for plastics and paints.
 9. A methodfor stabilization of organic material with respect to exposure to light,oxygen, and heat, adding a mixture according to claim 1 to the organicmaterial.
 10. A method for stabilization of plastics and paints withrespect to exposure to light, oxygen, and heat, adding a mixtureaccording to claim 1 to the plastics, paint, or a combination thereof.11. A tape, comprising: a polypropylene; and a mixture, comprising (A)at least one oligomeric compound, comprising repeat units of the formula(I),

wherein: R¹ is hydrogen, C₁-C₆-alkyl, formyl, C₂-C₆-alkanoyl,C₁-C₁₂-alkoxy, C₅-C₆-cycloalkoxy, cyanomethyl, 2-hydroxyethyl, benzyl ora radical of the formula —CR′═CH—CO—OR″, wherein R′ is hydrogen,C₁-C₆-alkyl or a radical of the formula —CO—OR″, and R″ is C₁-C₁₈-alkyl,C₅-C₈-cycloalkyl, C₇-C₁₈-aralkyl, phenyl, or tolyl; R² is a mixturecomposed of C₁₄-C₂₈-alkyl groups, where two of these alkyl groups whosenumber of carbon atoms is not permitted to differ by more than tworespectively make up at least 30% of this mixture; R³ and R⁴,independently of one another, are C₁-C₆-alkyl; and (B) at least onecompound of the formula (II) or (III)

wherein: n and m, independently of one another, are a natural numberfrom 2 to 22, and R¹, R³ and R⁴, independently of one another, are asdefined in formula (I).
 12. The tape according to claim 11, wherein: R¹is H, C₁-C₆-alkyl, formyl, acyl, or benzyl; R² is a mixture composed ofC₁₆-C₂₄-alkyl groups; R³ and R⁴ are methyl; and m and n are a naturalnumber from 6 to
 8. 13. The tape according to claim 11, whereincomponent A is an oligomer of formula (Ia):

and component B has been selected from the group of the compounds (IIa),(IIIa), and (IIIb):